Joint Research Centre The European Commission’s in-house science service Perfluorinated Chemicals, especially Perfluorinated Alkyl Sulfonates and Carboxylats: European Distribution and Legislation Robert LOOS [email protected] Directorate H - Institute for Environment and Sustainability Water Resources Unit (H.01) Ispra, Italy Outline Introduction Acronyms, Use of PFASs, Sources / Precursors / Emissions, Contamination Legislation Voluntary phase-out, Restriction of PFOS in Europe, Stockholm Convention, WFD, Directive 2013/39/EU Occurrence General, Surface waters, European Hotspots, Rhine River, The Sauerland Case, Groundwater, Tap / Drinking Water JRC EU-wide Monitoring Surveys Surface waters, Po River, Danube River, Groundwater, PFOS Modelling, Adriatic Sea Conclusions 21 October 2013 2 Acronyms • Term “PFCs” was used for substances such as PFOS or PFOA. • Term “perfluorinated chemicals” includes a wide range of chemicals with varied uses, characteristics and environmental profiles. • “PFCs”: first used to describe perfluorocarbons, a family of greenhouse gases (CF4), in official Kyoto Protocol documents. • Acronym “PFASs” (singular PFAS) should be used for “perfluoroalkyl and polyfluoroalkyl substances” such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). Buck, R.C., Franklin, J., Berger, U., Conder, J.M., Cousins, I.T., de Voogt, P., Astrup Jensen, A., Kannan, K., Mabury, S.A., van Leeuwen, S.P.J. Perfluoroalkyl and polyfluoroalkyl substances in the environment: Terminology, classification, and origins. Integrated Environmental Assessment and Management 7(4) (2011) 513–541. 21 October 2013 3 Use of PFASs • Since 1950, PFASs, surfactants and polymers made with the aid of PFASs have been widely used in numerous industrial and commercial applications. • C–F bond is extremely strong and stable. • Chemical and thermal stability of a perfluoroalkyl moiety, in addition to its hydrophobic and lipophobic nature, lead to highly useful and enduring properties in surfactants and polymers. • Polymer applications include textile repellents, stain-resistant coatings for carpets and grease-proof food-contact paper. • Surfactant applications that take advantage of the aqueous surface tension–lowering properties include processing aids for fluoropolymer manufacture, and aqueous film–forming foams (AFFFs) used to extinguish fires. 21 October 2013 4 Use of PFASs Water and oil repellents (impregnation) for carpets, leather, paper, textiles, food packaging Firefighting foams Inks, varnishes, waxes, metal plating and cleaning, coating formulations, lubricants, photography, photolithography, and semiconductor industries, hydraulic fluids 21 October 2013 5 Sources / Precursors • Widespread use of industrial raw materials and consumer products and articles. • Contain PFASs (also as impurities) • Perfluoroalkyl moiety in polymers or precursors degrades in the environment to form PFOS, PFOA, and similar substances. • Precursor substances: • Perfluorooctane sulfonamides (PFOSA) • N-ethyl perfluorooctane sulfonamidoethanol (NEt-FOSE) • Fluorotelomer alcohols (FTOHs) • Polyfluoroalkyl phosphate esters (PAPs) (phosphoric acids) 21 October 2013 6 Chemical Structures PFOA PFOS Perfluorooctanesulfonamide (PFOSA) was an ingredient in 3M’s former Scotchgard stain protection formulation. N-ethyl Perfluorooctane sulfonamidoethanol (NEtFOSE) 8:2 Fluorotelomer alcohol: volatile precursor of PFACs Polyfluoroalkyl phosphate esters (PAPs) (phosphoric acids) 21 October 2013 7 Sources and Emissions • Main sources of PFASs to the aquatic environment are municipal and industrial wastewater treatment plants. • Direct discharges • Landfill leachates • PFOA: released directly from fluoropolymer production plants. • Indirect emissions: caused by atmospheric degradation of the precursor compounds. 21 October 2013 8 Worldwide Contamination • Widespread use of PFASs / Emissions. • Broad range of these substances have been detected in the environment, wildlife, and humans. • The global extent of this contamination was first demonstrated for PFOS in wildlife (fish, birds, and marine mammals) by Giesy and Kannan (2001). • Human blood by Hansen et al. (2001). • PFASs: ubiquitously found in the (aqueous) environment. Giesy JP, Kannan K. Global distribution of perfluorooctane sulfonate in wildlife. Environ. Sci. Technol. 35 (2001) 1339–1342. Hansen KJ, et al. Compound-specific, quantitative characterization of organic fluorochemicals in biological matrices Environ. Sci. Technol. 35 (2001) 766-770. 21 October 2013 9 Voluntary phase-out of PFOS / PFOA production Concerns about the potential environmental and toxicological impact of long-chain PFASs: 1) The voluntary phase-out of production of PFOS and related compounds by their major global manufacturer in 2000 (3M Company). 2) Stewardship agreement launched in 2006 between the USEPA and 8 leading global companies to reduce emissions and product content of PFOA and related chemicals by 95% by 2010 and to work toward their elimination by 2015. 21 October 2013 10 Legislation in Europe • 2006: European Union Marketing and Use Directive restricting the use of „„perfluorooctane sulfonates‟‟ in the European Union. • 2009: Inclusion of PFOS in the Stockholm Convention on Persistent Organic Pollutants as an Annex B substance, i.e., restricted in its use. • 2013: PFOS becomes priority substance under the WFD. 21 October 2013 11 Marketing of PFOS restricted 21 October 2013 • Industries which cannot operate without PFOS are bound to use the best available techniques (BAT) to reduce emissions to the environment. • Consumer products and articles may not contain more than 0.1% of PFOS. 12 • Scientific opinion of EFSA considered it unlikely that adverse effects of PFOS and PFOA are occurring in the general population. • Uncertainties with regard to developmental effects in living organisms. • EFSA recommended that further data on PFASs levels in food and in humans would be desirable. 21 October 2013 13 Directive 2013/39/EU – Priority Substances Perfluorooctansulfonic acid (PFOS) EQS:0.65 ng/L (0.13 ng/L) Biota: 9.1 µg/kg • Expert laboratories can achieve LOQs of 0.1 ng/L • Biota EQS (9.1 µg/kg) is more easy to achieve 21 October 2013 14 Occurrence in Europe • Central and south European rivers have higher concentrations and mass discharges of PFASs than Northern European countries. • High PFASs levels in groundwater are often restricted to some contaminated areas, e.g., due to illegal waste deposition on agricultural land or in the vicinity of a fluoropolymer producing factory. • Sites with former fire-fighting activities are also potential “hot spot” areas. • Concentrations in drinking water remain fairly low on average. • Typical concentrations are in the low ng/L range with the exception of highly contaminated areas, like in the Moehne and Ruhr area in Germany. Eschauzier, C., de Voogt, P., Brauch, H.-J., Lange, F.T. Polyfluorinated chemicals in European surface waters, ground- and drinking waters. In: Polyfluorinated chemicals and transformation products, Hdb Env. Chem. 17 (2012) 73–102; Springer-Verlag, Berlin, Heidelberg. 21 October 2013 15 Surface waters • Rhone, Rhine, Danube, and Po rivers have the highest discharges of European rivers (between 810 and 2,200 m3/s) and in part also high PFASs concentrations, thus generating a considerable mass flux even at low water contamination levels. • Rhine: PFOS and PFOA < 10 ng/L. • PFBA and PFBS were found at high concentrations (335 and 181 ng/L). • At the Dutch–German border at Lobith high concentrations of PFBA and PFBS were observed in 2008 with average concentrations of 70 and 47 ng/L. Eschauzier, C., de Voogt, P., Brauch, H.-J., Lange, F.T. Polyfluorinated chemicals in European surface waters, ground- and drinking waters. In: Polyfluorinated chemicals and transformation products. Hdb Env. Chem. 17 (2012) 73–102; Springer-Verlag, Berlin, Heidelberg. Möller, A., et al. Distribution and sources of polyfluoroalkyl substances (PFAS) in the River Rhine watershed. Environmental Pollution 158 (2010) 3243-3250. 21 October 2013 16 PFOS in the Rhine River Eschauzier, C., de Voogt, P., Brauch, H.-J., Lange, F.T. Polyfluorinated chemicals in European surface waters, ground- and drinking waters. In: Polyfluorinated chemicals and transformation products, Hdb Env. Chem. 17 (2012) 73–102; SpringerVerlag, Berlin, Heidelberg. 21 October 2013 17 Surface waters • Elbe River: PFOS 6.4 ng/L (in 2008) • Predominating diffuse PFASs inputs, PFOS to PFOA ratio of 3:1 can be deduced. • Alz River (south Germany) • PFOA: up to 7.5 µg/L in the vicinity of a fluoropolymer manufacturing facility in Gendorf (in 2007). • Inn and Danube: concentrations of 100 and 50 ng/L PFOA. Eschauzier, C., de Voogt, P., Brauch, H.-J., Lange, F.T. Polyfluorinated chemicals in European surface waters, ground- and drinking waters. In: Polyfluorinated chemicals and transformation products, Hdb Env. Chem. 17 (2012) 73–102; Springer-Verlag, Berlin, Heidelberg. 21 October 2013 18 PFASs Hotspots Rhine: PFBA and PFBS Aare: PFBS Sauerland (Möhne/Ruhr): PFOS/A . Alz/Inn (Gendorf): PFOA PFBA/PFBS PFOS/PFOA . . River Scheldt (BE/NL) PFOS/PFOA Rhone / Seine (Fr) PFOS Barcelona; Llobregat River Cologne: Groundwater (PFOS) (Fire brigade training area) . 21 October 2013 . PFBS PFOA Eschauzier, C., de Voogt, P., Brauch, H.-J., Lange, F.T. Polyfluorinated chemicals in European surface waters, groundand drinking waters. In: Polyfluorinated chemicals and transformation products, Hdb Env. Chem. 17 (2012) 73–102; Springer-Verlag, Berlin, Heidelberg. 19 4,8-Dioxa-3H-Perfluorononanoate • • • 21 October 2013 ADONA, Ammonium 4,8-dioxa3H-perfluorononanoate, is 3M's PFOA replacement in the emulsion polymerization of fluoropolymers. Most of the ADONA used in fluoropolymer manufacturing is either recaptured from waste streams and products for reuse or is thermally destroyed during processing. These fluoropolymers are sintered onto the substrate at temperatures exceeding 280°C. ADONA decomposes at approximately 125– 175°C. 20 The Sauerland Case, Germany Environ. Sci. Technol. 45 (2011) 8046–8052. 21 October 2013 21 The Sauerland Case, Germany • Surface waters along the River Möhne became contaminated with PFCs, mainly by application of polluted soil conditioner on agricultural lands. • Soil conditioner (53,000 tons) has been distributed on more than 1300 farm lands between 2000 and 2006. • Maximum PFOA and PFOS concentrations were 2.4 and 33 mg/kg. • Contamination of drinking water. • Whereas soil samples contained more PFOS than PFOA, PFOA was the predominant compound observed in drinking water (2006: 500-640 ng PFOA/L). • A human biomonitoring study was implemented, which revealed 4-8-fold increased PFOA blood concentrations in residents exposed to contaminated drinking water compared to a reference population. 21 October 2013 Hölzer et al., Environ. Sci. Technol. 45 (2011) 8046–8052. Hölzer et al., Environ. Health Perspect. 116 (5) (2008) 651-657. 22 The Sauerland Case, Germany • Fish samples of Lake Möhne PFOS was the predominant PFAS found Highest median PFOS concentrations: Perches (median: 96 ng/g), Eels (77 ng/g), Pikes (37 ng/g) Whitefish (34 ng/g), Roaches (6.1 ng/g) • PFOS concentrations in blood plasma of anglers Ranged from 1.1 to 650 μg/L (PFOA: 2.1-170 μg/L; PFHxS: 0.4-17 μg/L). • A distinct dose-dependent relationship between fish consumption and internal exposure to PFOS was observed. • PFOS concentrations in blood plasma of anglers consuming fish 2-3 times per month were 7 times higher compared to those without any fish consumption from Lake Möhne. 21 October 2013 Hölzer et al., Environ. Sci. Technol. 45 (2011) 8046–8052. Hölzer et al., Environ. Health Perspect. 116 (5) (2008) 651-657. 23 Groundwater • Bavaria, industrial area Gendorf, Alztal aquifer, Germany: Groundwater contamination with PFOA: up to 7 µg/L. • near Cologne, Germany. The source of the contamination was identified to be a fire brigade training area (AFFFs). ΣPFASs reached levels up to 4 µg/L, with PFOS and PFHxS prevailing. Eschauzier, C., de Voogt, P., Brauch, H.-J., Lange, F.T. Polyfluorinated chemicals in European surface waters, ground- and drinking waters. In: Polyfluorinated chemicals and transformation products, Hdb Env. Chem. 17 (2012) 73–102; Springer-Verlag, Berlin, Heidelberg. 21 October 2013 24 Tap / Drinking Water Barcelona: PFOA 9 ng/L; PFOS 50 ng/L Amsterdam: PFBA <9.5 to 52 ng/L, PFBS 11 to 42 ng/L Ericson, I., et al. Levels of perfluorinated chemicals in municipal drinking water from Catalonia, Spain: public health implications. Arch. Environ. Contam. Toxicol. 57 (2009) 631–638. Ullah, S., Alsberg, T., Berger, U. Simultaneous determination of perfluoroalkyl phosphonates, carboxylates, and sulfonates in drinking water. Journal of Chromatography A 1218 (2011) 6388– 6395. Eschauzier, C., et al. Impact of treatment processes on the removal of perfluoroalkyl acids from the drinking water production chain. Environ. Sci. Technol. 46 (2012) 1708−1715. 21 October 2013 25 JRC EU-wide Monitoring Surveys • 2007: Surface water survey “EU-wide survey of polar organic persistent pollutants in European river waters” Environmental Pollution 157 (2009) 561–568 • Joint Danube Survey (2007) Water Research 44 (2010) 2325–2335 • 2008: Groundwater survey “Pan-European survey on the occurrence of selected polar organic persistent pollutants in ground water” Water Research 44 (2010) 4115–4126 • 2010: Waste water treatment plant (WWTP) effluents Water Research, in press • 2012: Pilot exercise for WFD “Watch List” (surface waters) 21 October 2013 26 Sampling Stations: Rivers and Groundwater Focus on “emerging pollutants” Surface water: 122 samples Ground water: 164 samples Danube and tributaries: 103 samples Autotrace 280 system 21 October 2013 28 LC-MS-MS at JRC-IES Ispra LC-MS-MS UHPLC-MS-MS Ultra-high pressure liquid chromatography Particles < 2 mm Higher pressure; faster; more efficient 21 October 2013 29 Median concentrations [ng/L] The most frequently detected compounds were 1-nitrophenol (freq 97%), NPE1C (97%), PFOA (97%), caffeine (95%), carbamazepine (95%), PFOS (94%), benzotriazole (94%), 2,4-dinitrophenol (86%), diclofenac (83%), and tolyltriazole (81%). The highest median concentrations were measured for NPE1C (233 ng/L), benzotriazole (226 ng/L), tolyltriazole (140 ng/L), carbamazepine (75 ng/L), and caffeine (72 ng/L). M Be N P et E hy nzo 1C lb tri e a C nz zo ar ot le ba ria m zo az le ep C i ne a Su Ni ffei t lfa rop ne m 2, et hen 4- ho o l Di ni xaz tro o ph le en D ol iu ro PF n Ib OS up D rof icl e of n e N na D ap c es r et B e o x hy n e lte taz n rb o ut ne y Is laz op i n e r Be otu za ron fib ra te PF O A Te 2 rb ,4ut yl D az At ine ra zi n PF e N PF A H pA PF D PF A Ke U to nA p M rofe ec n G op r em o fib p ro D z es et PFH il hy la xA tra Si zin m e Bi az sp in h e N en on ol yl A ph en o te rt- l O Es P tro ne PFOA PFOS ph e n NP ol E1 C PF Ca Ca OA rb a m ffe i ne a Be ze nz pi n e ot ria zo 2, 4le Di P ni tr o F OS ph M e et hy Dic nol lo lb Su enz fena lfa otr c ia m z et ho ole Is xaz op ol ro e tu ro Di n ur on Be PFN De nt A az se Na one th yl p te rb rox en ut yl az in Te Atra e rb ut zine yla zin PF e Ib Hp up A Be rof za en fib ra De te se 2, th 4yl D at ra z M ec ine op ro p PF D P A G FH e m xA Bi fibr oz sp i h No en l ny ol A lp he no PF l Un Si m A az Es ine Ke tro to n e O pro ct ylp fen he no l Ni tr o Frequency of detection [%] EU-wide Survey of Polar Pollutants in Rivers 100 90 80 Average frequency of detection: 62 % 70 60 50 40 30 20 10 0 PFNA 6 ng/L PFOS PFHpA 250 200 150 100 50 3 ng/L 0 PFOA Loos et al., Environ. Poll. 157 (2009) 561-568. Danube River 21 October 2013 31 Danube River (2007) PFOA/S 70 Germany Austria Slovakia Hungary Serbia Romania / Bulgaria 60 50 PFOA (Tributaries) 40 PFOS (Danube) 30 Concentration [ng/L] PFOA (Danube) Inn River 20 10 0 2500 2000 1500 1000 500 0 River km PFOA 21 October 2013 PFOS 32 River Aire (UK) PFOS: 10-15 ng/L JRC cooperation with Lancaster University (Mark Earnshaw, Alex Paul, Andy Sweetman, Kevin Jones) 21 October 2013 33 Groundwater PFOA PFOS PFHxS PFHpA 21 October 2013 34 21 October 2013 hy la t et ra z C e in e N PE 1 2, PFOS PF O A p fe n pr o ec o M no l no l ph e op ro Ke t S EE T D PF O ph e itr o N in itr o 4D ar C Bi sp he no lA ba m az ep in e At ra zi ne D Si es m et az hy in lte e rb ut yl az in e Be nt az on N e on yl ph en ol es zo l ria e le fe in Number of detections > 0.1 mg/L D zo t Be n zo 0 af ria ot 5 C 10 Number of conc. levels > 10 ng/L 15 en z 20 yl b pr op ne fe i or hl D ic T e in D EE af C en e e os e al la z ut y cr of pr to Su rb lte in nt az on Number of conc. levels > 0.1 mg/L 25 M et h et hy es Ke yl le zo ep m az e ol en tri a zo Be C ar ba en zi n m id en ph tra e zo l fa es ph ld hy lb hy la N on yl et hy es m et et M on - D az or id C hl D ls ul hy im et 1C no lA nz ot ria he yl en PE N sp h sp de Bi on - Be az ,N -D N or id hl C Groundwater Number of detections > 10 ng/L 30 70 60 50 40 30 20 10 0 PFOA 35 Max. Concentrations in Groundwater 12000 42 Average frequency of detection for all compounds: 25% 32 Frequency of detection [%] 8000 6000 4000 2000 11 5 10 40 4 53 13 34 18 52 55 84 7 42 2 29 49 56 21 83 20 48 43 29 6 0 N Be PE n 1C N tazo on yl n e p D he n ic ol hl o Ke rpr t o op Bi pro sp fe he n n Su ol A Be cra n z los ot e ria z M ol e Te c o e rb pro ut yl p M a et He zi n h y xa e lb z en i no D es zot ne et ri a hy zo la l tra e zi ne D E C Ibu E T ar p ba ro m fen az ep in Li e D nu es ro et hy n D l te rb iu ro ut yl n az At ine r M azin et ol e ac hl C o af r N fei n itr op e he no PF l O 2, S 4 S M -D i ma et in h a itr zin be op e nz he th no l ia zu ro n Concentration [ng/L] 10000 Not included: Dimethylsulfamid (max. 52 mg/L in one sample; freq. 12%), Chloridazon-desphenyl (max. 13 mg/L; freq. 17%), Chloridazon-methyldesphenyl (max. 1.2 mg/L; freq. 6%), PFOA (max. 39 ng/L; freq. 66 %). Loos et al. Pan-European survey on the occurrence of selected polar organic persistent pollutants in ground water. Water Res. 44 (2010) 4115-4126. 21 October 2013 36 Modelling-based assessment of PFOA and PFOS emissions • 46 river monitoring points for rivers which “discharge” into the seas • Around the same number of relevant rivers / streams (~50) is missing 21 October 2013 37 Correlation of PFOA/S with Population PFOS PFOA 1.0E+01 1.0E+01 1.0E+00 1.0E+00 all samples: Emission factor 82 ug/inhab./day maximum reported emission factor 57 ug/inhab./day 1.0E-01 1.0E-02 PFOA discharge (tonnes/year) PFOS discharge (tonnes/year) 1.0E-01 samples: emission factor 27.4 ug/inhab./day 1.0E-03 1.0E-04 WWTP in Germany: Emission factor 30 ug/inhab./day only samples with E<0.5 t/y: Emission factor 19.2 ug/inhab./day 1.0E-03 1.0E-04 1.0E-05 1.0E-06 1.E+03 1.0E-02 1.0E-05 1.E+04 1.E+05 1.E+06 1.E+07 1.0E-06 1.E+03 1.E+08 population (inhab.) WWTP in Switzerland: Emission factor 12 ug/inhab./day 1.E+04 1.E+05 1.E+06 1.E+07 1.E+08 population (inhab.) Estimation for the year 2007: PFOS and PFOA discharges along the whole European river network to coastal areas in Europe: ~ 20 t/a PFOS and 30 t/a PFOA. Emission factor: 27 mg/day/person PFOS, and 82 mg/day/person PFOA. A. Pistocchi, R. Loos, Environ. Sci. Technol. 43 (2009) 9237-9244. 21 October 2013 38 Adriatic Sea Water samples taken in 2011/12. 21 October 2013 39 Adriatic Sea Venice, 16 km off-shore Acqua Alta Oceanographic Platform (CNR) Water depth: 16 m 21 October 2013 http://www.ismar.cnr.it/infrastrutture/piattaforma-acqua-alta/ 40 1H-Benzotriazole 5-Methyl-1H-benzotriazole Alachlor Atenolol Atrazine Atrazine-desethyl Atrazine-desisopropyl Carbamazepine Carbendazim Chloridazon DEET Diuron Irgarol Isoproturon Linuron Metolachlor Metoprolol Simazine Sulfadimethoxine Sulfamethoxazole Terbutryn Terbutylazine Terbutylazine-desethyl 2,4-D 2,4,5-T Bentazone Bezafibrate Clofibric acid Dichlorprop Gemfibrozil Ibuprofen MCPA Mecoprop Naproxen Sucralose PFPA PFHxA PFHpA PFOA PFNA PFDA PFHxS PFOS Concentration [ng/l] Adriatic Sea 20 18 10. Feb 11 16 6 May 2011 15. Sep 11 14 13 March 2012 12 10 8 6 4 2 0 21 October 2013 41 Adriatic Sea Highest Concentrations (max.) Caffeine 367 ng/l Nitrophenol 36 ng/l 2,4-Dinitrophenol 34 ng/l 5-Methyl-1H-benzotriazole 18.5 ng/l Sucralose 11.1 ng/l 1H-Benzotriazole 9.2 ng/l Terbutylazine 9 ng/l Alachlor (one sample) 7.7 ng/l Atrazine-desisopropyl 6.6 ng/l DEET 5.0 ng/l Terbutylazine-desethyl 4.3 ng/l 21 October 2013 Metolachlor PFOA Linuron PFPeA PFHxA Diuron Simazine PFHxS Atrazine PFOS Chloridazon Ibuprofen Carbendazim Sulfamethoxazole 2.8 ng/l 2.5 ng/l 2.3 ng/l 2.3 ng/l 2.2 ng/l 2.0 ng/l 1.6 ng/l 1.6 ng/l 1.5 ng/l 1.3 ng/l 1.3 ng/l 1.1 ng/l 1.1 ng/l 1.0 ng/l 42 PFOA and PFOS in Oceans Chemical Adriatic Sea Literature PFOA 0.79 – 2.51 ng/l North Sea: 0.11–7.8 ng/l (Ahrens et al. 2009. Chemosphere 76, 179-184; Möller et al. 2010. Environ. Pollut. 158, 3243-3250; Willie et al. 2010. J. Chromatogr. A 1217, 6616–6622) China (Pacific; coastal): 38-1542 pg/l (Cai et al. 2012. Environ. Pollut. 161, 162-169) Catalonian Coast: <0.08-1.86 ng/l (Sánchez-Avila et al. 2010. Mar. Pollut. Bull. 60 (1), 103–112) Atlantic Ocean: 229-439 pg/l (max.) (Ahrens et al. 2009. ES&T 43, 3122–3127; Yamashita et al. 2005. Mar. Pollut. Bull. 51, 658–668) PFOS 21 October 2013 1.34 ng/l North Sea: 0.25-4.2 ng/L China (Pacific; coastal): <20.7-70.3 pg/l Catalonian Coast: <0.03-3.93 ng/L Atlantic Ocean: 73-291 pg/l (max.) 43 PFASs in Aquatic Biota Environ. Sci. Technol. 45, 2011, 7962–7973. Harbor seals in the German Bight PFOS: predominant compound with a maximum concentration of 3676 ng/g. Ahrens, L.; Siebert, U.; Ebinghaus, R. Total body burden and tissue distribution of polyfluorinated compounds in harbor seals (Phoca vitulina) from the German Bight. Mar. Pollut. Bull. 2009, 58, 520–525. 21 October 2013 44 PFASs in Fish PFASs in wild fish from Northern Germany Fish filet samples (eels, bream, herring, mackerel, carp, trout) PFOS was found in the filet samples caught from densely populated regions at levels between 8.2 and 225 µg/kg. Marine or remote locations: PFOS: up to 50.8 µg/kg. Schuetze, A.; Heberer, T.; Effkemann, S.; Juergensen, S. Occurrence and assessment of perfluorinated chemicals in wild fish . PFASs in muscle tissue from edible fish species from the second largest freshwater lake in Sweden, Lake Vättern (LV), and in brackish water of the Baltic Sea PFOS concentrations were higher in LV (medians 2.9–12 ng/g) than in Baltic Sea water fish (medians 1.0–2.5 ng/g). from Northern Germany. Chemosphere 2010, 78, 647–652 Berger,U.;Glynn,A.;Holmstrom, K.E.;Berglund,M.;Ankarberg, E. H.; Tornkvist, A. fish consumption as a source of human exposure to perfluorinated alkyl substances in Sweden: Analysis of edible fish from Lake Vattern and the Baltic Sea. Chemosphere 2009, 76, 799–804. PFASs in high mountain lakes in France PFOS: 3.61–4.24 ng/g. Ahrens, L.; Marusczak, N.; Rubarth, J.; Dommergue, A.; Nedjai, R.; Ferrari, C.; Ebinghaus, R. Distribution of perfluoroalkyl compounds and mercury in fish liver from high-mountain lakes in France originating from atmospheric deposition. Environ. Chem. 2010, 7, 422–428. 21 October 2013 45 Conclusions • Lack of monitoring data (spatial and temporal variability) • The JRC focuses its monitoring on EU-wide studies • Important for the prioritization of chemicals • Next year the JRC will take over the lead on the prioritization under the WFD • Monitoring data, effect data, and modelling • PFOS compliance monitoring (EQS: 0.65 ng/L) • Biota EQS: 9.1 µg/kg 21 October 2013 46 Conclusions • Dietary intake is supposed to be an important path of exposure for the general population to PFOS and PFOA. • Contamination of drinking water led to significantly increased PFOA concentrations, in blood samples of the affected populations in Little Hocking, Ohio, USA, Arnsberg, Germany, and Minnesota, USA. • Fish is an important part of the diet and recently the significance of fish consumption on the internal exposure to PFOS was emphasized. • Continued use of PFOA and PFOS precursors 21 October 2013 47 “Polar Bear Brains have High Levels of Environment Toxins” Nature World News; 24 July 2013 Greaves, A.K., et al. BRAIN REGION DISTRIBUTION AND PATTERNS OF BIOACCUMULATIVE PERFLUOROALKYL CARBOXYLATES AND SULFONATES IN EAST GREENLAND POLAR BEARS (URSUS MARITIMUS) Environmental Toxicology and Chemistry, Vol. 32, No. 3, 2013, pp. 713–722. 21 October 2013 48 Thank you for your attention ! Monte Rosa (4.634 m) Lago Maggiore Ispra JRC 21 October 2013 49